Organoaluminum activators on clays

Abstract

This invention relates to organoaluminum activators, organoaluminum activator systems, preferably supported, to polymerization catalyst systems containing these activator systems and to polymerization processes utilizing the same. In particular, this invention relates to catalyst systems comprising an ion-exchange layered silicate, an organoaluminum activator, and a metallocene.

What is claimed is: 
     
       1. A catalyst system comprising an ion-exchange layered silicate, a catalyst compound, and an organoaluminum activator represented by the formula:
   (R 1   2 —Al—R 3 ) q —X—R* y  
 
 wherein each R 1 , independently, is a C 1 -C 40  alkyl group; 
 each R 3 , independently, is a C 2 -C 20  hydrocarbon; 
 each R*, independently, is a hydrogen atom or a C 1 -C 40  alkyl group; 
 X is carbon or silicon; 
 y is 0, 1, 2, or 3; 
 q is 1, 2, 3, or 4; 
 wherein q+y=4; and 
 wherein q is 2, 3, or 4 if X is carbon. 
 
     
     
       2. The catalyst system of  claim 1 , wherein one or more R 3  hydrocarbons is represented by the formula:
   —(CH 2 ) n —
 
 where n is an integer from 2 to 20. 
 
     
     
       3. The catalyst system of  claim 1 , wherein one or more R 1  groups is methyl, ethyl, propyl, isobutyl, butyl, hexyl, or octyl. 
     
     
       4. The catalyst system of  claim 1 , wherein q=2. 
     
     
       5. The catalyst system of  claim 1 , wherein q=4. 
     
     
       6. The catalyst system of  claim 1 , wherein the ion-exchanged layered silicate is selected from the group consisting of montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, stevensite, vermiculite, halloysite, aluminate oxides, bentonite, kaolinite, dickite, smectic clays, mica, magadiite, kenyaite, octosilicate, kanemite, makatite, attapulgite, sepiolite, zeolitic layered materials, and mixtures thereof. 
     
     
       7. The catalyst system of  claim 1 , wherein the ion-exchanged layered silicate is selected from the group consisting of dickite, nacrite, kaolinite, metahalloysite, halloysite, chrysotile, lizardite, antigorite, montmorillonite, beidellite, nontronite, saponite, hectorite, stephensite, vermiculite, mica, illite, sericite, glauconite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorites, and mixtures thereof. 
     
     
       8. The catalyst system of  claim 1 , wherein the ion-exchanged layered silicate comprises montomorillonite. 
     
     
       9. The catalyst system of  claim 1 , wherein a combination of the ion-exchanged layered silicate and an inorganic oxide is spray dried prior to contact with the organoaluminum activator. 
     
     
       10. The catalyst system of  claim 1 , wherein the catalyst compound is a metallocene catalyst. 
     
     
       11. The catalyst system of  claim 10 , wherein the catalyst compound is Me 2 Si(2,3,4,5-tetramethylCp)(Ind)ZrMe 2 . 
     
     
       12. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of  claim 1 . 
     
     
       13. The process of  claim 12 , wherein the monomer comprises ethylene and/or propylene. 
     
     
       14. The process of  claim 12 , wherein the polymerization is conducted in gas phase or as a slurry. 
     
     
       15. A composition comprising the reaction product of (i) a trialkyl aluminum or a dialkyl aluminum hydride and (ii) an alkene terminated compound, wherein the alkene terminated compound has at least two alkene termini, and the alkene terminated compound is a multivinylsilane. 
     
     
       16. A composition comprising the reaction product of:
 (i) an alkyl aluminum represented by the formula:
   AlR 3    
 
 
       wherein each R is independently, a hydrogen atom or a substituted or unsubstituted alkyl group and/or a substituted or unsubstituted aryl group; and
 (ii) an alkene terminated compound represented by the formula:
   X(R′) 4-v (R 4 ) v  
 
 
 
       wherein X is Si, R 4  is a hydrocarbenyl group containing 2 to 20 carbon atoms having an alkene terminus, R′ is a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms, v is 1, 2, 3, or 4. 
     
     
       17. The composition of  claim 16 , wherein the alkyl aluminum is diisobutyl aluminum hydride. 
     
     
       18. The composition of  claim 16 , wherein the alkene terminated compound has at least two alkene termini. 
     
     
       19. A composition comprising the reaction product of:
 (i) an alkyl aluminum represented by the formula:
   AlR 3    
 
 
       wherein each R is independently, a hydrogen atom or a substituted or unsubstituted alkyl group and/or a substituted or unsubstituted aryl group; and
 (ii) an alkene terminated compound represented by the formula:
   X(R′) 4-v (R 4 ) v  
 
 
 
       wherein X is Si or C, R 4  is a hydrocarbenyl group containing 2 to 20 carbon atoms having an alkene terminus, R′ is a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms, v is 1, 2, 3, or 4 if X is Si, and v is 2, 3, or 4 if X is C wherein the alkene terminated compound has at least two alkene termini and the alkene terminated compound is a multivinylsilane. 
     
     
       20. The composition of  claim 19 , wherein the multivinylsilane is selected from the group consisting of tetravinylsilane, methyltrivinylsilane, dimethyldivinylsilane, diethyldivinylsilane, di-n-dodecyldivinylsilane, cyclohexyltrivinylsilane, phenyltrivinylsilane, methylphenyldivinylsilane, benzyltrivinylsilane, and (3-ethylcyclohexyl) (3-n-butylphenyl)divinylsilane. 
     
     
       21. A composition comprising the formula:
   (R 1   2 —Al—R 3 ) q —X—R* y  
 
 wherein each R 1 , independently, is a C 1 -C 40  alkyl group; 
 each R 3 , independently, is a C 2 -C 20  hydrocarbon; 
 each R*, independently, is a hydrogen atom or a C 1 -C 40  alkyl group; 
 X is silicon; 
 y is 0, 1, 2, or 3; 
 q is 1, 2, 3, or 4; 
 wherein q+y=4; and 
 wherein q is 2, 3. 
 
     
     
       22. A supported activator comprising an ion-exchange layered silicate and the composition of  claim 20 . 
     
     
       23. The supported activator of  claim 22 , further comprising a metallocene catalyst. 
     
     
       24. The supported activator of  claim 22 , wherein non-coordinating anion is absent. 
     
     
       25. The supported activator of  claim 22 , wherein alumoxane is absent. 
     
     
       26. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of  claim 2 , wherein one or more R 1  groups is methyl, ethyl, propyl, isobutyl, butyl, hexyl, or octyl. 
     
     
       27. The process of  claim 26 , wherein the monomer comprises ethylene and/or propylene. 
     
     
       28. The process of  claim 26 , wherein the polymerization is conducted in gas phase or as a slurry. 
     
     
       29. The polymerization process of  claim 12 , where q is 2 or 4. 
     
     
       30. The process of  claim 29 , wherein the monomer comprises ethylene and/or propylene. 
     
     
       31. The process of  claim 29 , wherein the polymerization is conducted in gas phase or as a slurry. 
     
     
       32. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of  claim 9 . 
     
     
       33. The process of  claim 32 , wherein the monomer comprises ethylene and/or propylene. 
     
     
       34. The process of  claim 32 , wherein the polymerization is conducted in gas phase or as a slurry. 
     
     
       35. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of  claim 10 . 
     
     
       36. The process of  claim 35 , wherein the monomer comprises ethylene and/or propylene. 
     
     
       37. The process of  claim 35 , wherein the polymerization is conducted in gas phase or as a slurry. 
     
     
       38. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of  claim 10 , wherein the monomer comprises ethylene and/or propylene and the polymerization is conducted in gas phase or as a slurry. 
     
     
       39. A polymerization process comprising contacting one or more alkene monomers with the catalyst system of  claim 11 , wherein the monomer comprises ethylene and/or propylene and the polymerization is conducted in gas phase or as a slurry.